Ceramic decoration method



United States Patent CERAMIC nnconATIoN METHOD Christian C. Jessen,Perth Amhoy, N. J., assignor to E. I. du Pont de Nemours and Company,Wilmington, Del., a corporation of Delaware No Drawing. Application May13, 1950, Serial No. 161,903

9 Claims. (Cl. 117-40) This invention relates to the application ofceramic decorations to base objects and more particularly to thedecoration of such objects with ceramic colors by a squeegee printingmethod involving the application of multiple prints.

The squeegee or screen stencil method of applying ceramic decorations,e. g., glass colors composed of inorganic pigments and finely groundglass, to ceramic (glass, china, porcelain, etc.) and metal objects haslong been in use. This method of decorating glassware is now used ahnostuniversally throughout the beverage and milk bottle industry and to aconsiderable extent in the decoration of tumblers and the like objects.Present practice generally involves the use of a dispersion of thedecorating enamel in an oily vehicle containing a volatile solvent toform the squeegee paint. This type of vehicle has been used successfullyfor years in the preparation of squeegee paints but when a multi-coloreddecoration is desired all prints except the last must be dried to removethe volatile solvent and set the print before the next print can beapplied without smearing resulting. Following the printing operation,the object bearing the design is then fired to fuse the ceramicdecoration to the object.

A recent modification of the squeegee method involves the use of avehicle which is solid at normal temperatures but fluid at somewhatelevated temperature during squeegeeing. Certain vehicles of this typeand their use in t; e application of glass colors constitutes thesubject matter of my pending application Serial No. 79,301, filed March2, 1949, now U. S. Patent No. 2,607,701. Use of such vehicles isadvantageous in that the hot vehicle solid-ifies instantly upon contactwith the cold ware and obviates the necessity of a drying operationbetween successive applications of prints. However, the use of such ahotmelt vehicle for all applications in multiple-print operationsinvolves the possibility of damage to previous prints due to the heatfrom the succeeding hot application. The present invention is concernedwith a method whereby this dificulty is completely eliminated orsubstantially minimized.

It is an object of the invention to provide an improved method for theceramic decoration of base objects, particularly ceramic materials suchas glassware. A further object is an improvement in the application ofceramic decorations by the squeegee or screen stencil method where morethan one printing is involved and whereby the use of driers for theremoval of solvent from a printed design in order to solidify the designprior to application of a succeeding print is entirely eliminated. Stillother objects will be apparent from the following description.

The above objects are accomplished in accordance with the invention byapplying to a base object, particularly a ceramic object such as glass,china, porcelain or the like ware, one or more prints of a ceramicdecorating composition comprising a dispersion of a ceramic decorationin a vehicle of the type hereinafter defined which immediately uponcontact with the object solidifies to a firm, solid, adherent coating;and, without inter-mediate drying or firing said print or prints,applying a final print of a ceramic decorating composition comprising aceramic decoration dispersed in a vehicle which includes a volatilesolvent; and thereafter firing the printed object to fuse the decorationto the ware.

The decorating composition or compositions em loyed in the applicationof all but the last coating or print are applied to the ware employingthe well-known squeegee or screen stenc l technique. These compositionsare dispersions of ceramic decorations, such as finely ground mixturesof inorganic pigments and glass, in a vehicle which comprises: (a) 30 toof a material which melts within the temperature range to 230 E, whichmaterial may be a wax, a mixture of waxes, or a mixture of a wax orwaxes with a wax-like substance; (17) 1 to 10% of ethyl cellulose; (c)14 to 68% of resin or a rosin derivative or mixture of such substances;(d) 0.5 to 10% of an organic phosphate material such as lecithin orphosphorated tall oil; and (e) 0 to 1% of pyrogallic acid. Finely groundceramic decorations dispersed in such a vehicle in proportions of about2 to 6 parts by weight of the decoration to 1 part of the vehicleproduces decorating compositions which are solids at ordinary or normaltemperatures, are substantially non-volatile and can be applied readilyand successfully to the object to be decorated at a temperature withinthe range of 120 to ..30 F. through a stencil screen employing thesqueegee technique. At such temperatures the compositions are pastes orpaints and when applied to were which is at ordinary temperature theysolidify almost instantly to provide firm, solid, adherent coatingswhich require no drying or firing before the application of a subsequentprint. The temperature of the ware to which such a hot composition isapplied need not be at room temperature but should be at least about 15F. lower than the melting temperature of the composition being applied.In practice, however, the ware ordinarily will be at about roomtemperature.

Not all vehicles which melt within the range 120 to 230 F. are suitablefor use in applying the first decorating prints, i. e., all but the lastprint. In order for a vehicle to be suitable for this purpose it mustgive a squeegee paste or paint which is workable at about 120 to 230 F,i. e., it must not thicken or gel during long periods at the temperatureof application; its viscosity should not change substantially at suchtemperature; it should not clog the screen; and it should have properflow and leveling characteristics. This means that the vehicle should besubstantially non-volatile at the working temperature, yet it shouldvolatilize fast enough during firing to prevent running or slipping ofthe print. Furthermore, the vehicle must be one which solidifiesinstantly on application to the cold ware to" form a firm, smooth,tough, adherent coatin which is resistant to normal abrasion and shockand which is low in carbonaceous residue upon being fired. The vehiclealso must be sufiiciently tacky to adhere the print to the ware, but itmust not be so tacky as to cause pickup of a previous print on theunderside of a later color screen, e. g., during superimposition ofcolor prints. The vehicle should produce prints that are neither toohard nor too soft: if too hard, they fracture readily on handling; iftoo soft, they become marred, blurred and distorted readily. It has beendiscovered that to meet these requirements a vehicle must containcertain ingredients or types of ingredients which, furthermore, must bepresent in certain proportion ranges, as specified above.

The final application of ceramic decoration is made in accordance withthe invention employing a dispersion of a ceramic decoration in avehicle which is non-solid,

i. e., pasty or liquid, at ordinary temperatures. Such a vehicle may beof the type heretofore usually employed in the application of ceramicdecorations. They are hereinafter referred to as air-dry vehicles andwhen they contain a dispersed ceramic decoration the resultingcompositions are referred to as air-dry decorating compositions, asdistinguished from the hot-melt type vehicle or decorating compositionsdescribed above, since they are solidified by the removal of solvent, i.e., by drying in the air, in a drier or in the furnace.

The final coating of ceramic decoration dispersed in an air-dry vehiclemay be applied by various methods including spraying or brushing but ispreferably applied by the squeegee method. Air-dry vehicles suitable foruse in decorating compositions for the final print by squeegeeapplication usually contain bonding, viscosify ing and dispersing agentsin addition to a volatile solvent. Vehicles of the type described inDeyrup Patent 2,379,507 aresuitable and illustrative. However, air-dryvehicles of the following composition are preferred: (a) 50 to 80% of avolatile solvent, generally of the terpene or petroleum type such asterpene ethers, terpene alcohol and the aromatic and parafiinhydrocarbon solvents; (b) 15 to 35% of rosin or a rosin derivative ormixtures of such substances, which serve as binders; (c) 0.5 to 7% ofethyl cellulose which serves as a viscosifier and hardener; and (d) 0.5to 10% of an organic phosphate material such as lecithin or phosphoratedtall oil, which serve as wetting agents. The most effective amounts ofsuch wetting agents are about 4 to 10% for lecithin and 0.5 to 7% forphosphorated tall oil. Of these two substances the latter is preferred.Still other substances may be present in minor amounts.

The following Table 1 shows the compositions of five preferred vehiclesof the hot-melt type which are especially well-suited for use in theapplication of all but the last coating decoration, while Table 2 showsthe compositions of six preferred air-dry vehicles for use in thesqueegee application of the final coating decoration.

TABLE 1.HOT-MELT VEHICLES Composition Pyrogallic acid .i:

TABLE 2.AIR-DRY VEHICLES Composition F G H I i .T l K Polymerizedabietic acid 7. 98 15. .1 10. 03 10. Hydrogenated rosin 13. 60 6.58 20.1O 21. 11 11.03 11.10 Ethyl cellulose 2. 28 2. 28 3. 30 2. 39 3. 21 0.86Diethyl oxalate 3. 28 3. 28 3. 50 3. 66 3.67 3. 70 dl-Malic aoid O. 0.18 0. 20 0. 18 0. 18 0. 18 Terposol #3 12. 98 12.98 48. 44 Pine 0 a 30.00 31. 23 16.11 73. 31 Petroleum solvent 51. 96 51. 96 35. 60 Boric acid0. 40 0.37 10% Solution of 85% ortho pilimSphOfiC acid in pine o Dieselfuel Lecithin The Terposol #3 in some of the above compositions is acommercial terpene solvent described as a terpene ether obtained by thereaction of a terpene hydrocarbon with methanol. The Petroleum solventin some of the compositions Was either Solvesso #150" or Arosol #12,which are commercial solvents of the aromatic hydrocarbon type. i

The air-dry vehicles of Table 2 may be prepared by heating a mixture ofthe ingredients, other than the pine oil solution of phosphoric acid andthe lecithin or phosphorated tall oil, at a moderately elevatedtemperature, e. g. about 194 F., until the mixture is homogeneous. Themixture is then cooled somewhat, e. g. to about 106 F., and theremaining ingredients are added and the entire batch stirred untilhomogeneous. Squeegee paints using such vehicles are made by mixing 2 to6 parts of glass enamel with 1 part of vehicle and then passing .theresulting mixture through a roll mill, or other type of equipmentcommonly used to disperse ceramic pigments in vehicles, to obtain auniform paint. j

The hot-melt vehicles of Table 1 may be prepared by heating a mixture ofthe ingredients, other than the lecithin, phosphorated tall oil andpyrogallic acid, at an elevated temperature, e. g. about 266 F., untilthe mixture is homogeneous. The remaining ingredients are then added andthe entire batch is agitated at about the same temperature untilhomogeneous. Squeegee paints or pastes using these vehicles are made bymixing 2 to 6 parts of glass enamel with 1 part of the vehicle, thenpassing the resulting mixture through a roll mill or the like to obtaina uniform composition. ,The mixture will usually be kept at atemperature of about 176 to 230 F. during such processing. The paste orpaint may then be used directly or run into a shallow pan, allowed tosolidify and then broken up into lumps for shipment or storage.

The following examples illustrate the use of various of the abovevehicles in the application of ceramic decorations to glassware inaccordance with the invention. In

all cases the decorating paints were prepared using 2 to' 6 parts ofglass color per part of vehicle.

Example 1 room temperature until the paint was maintained at 120 to 230F. during the operation. A second print decoration, not superimposedover the first, was applied by the squeegee method using a glass colorpaint prepared with air-dry vehicle F of Table 2. In the second printingboth the ware and the paint were at room temperature. The printed wareWas then fired in the usual manner at a temperature necessary to fusethe decoration to the glass. No difliculty was encountered in applyingthe second print and an excellent final decoration resulted.

Example 2 The procedure of Example 1 was repeated except that the secondprint was superimposed over the first print and the paint used in thesecond printing was prepared with air-dry vehicle I of Table 2. Anexcellent decoration resulted and no damage to the first print resultedupon application of the second print. Similar results were obtained whenthe paint for the second or superimposed print was prepared employingair-dry vehicles .H, I or K of Table 2.

Example 3 The general procedure of Example 1 was repeated except thatthree printings of decoration were applied to the ware. Hot-melt vehicleB was used in preparing the paint for the first two prints, the secondof which was superimposed over the first. in preparing the paint for thefinal print which was superimposed over the first two prints. No damageto any of the prints resulted from the application of succeeding printsand an excellent final decoration resulted upon firing the printed wareto fuse the decoration to the glass. The same results were obtained whenair-dry vehicle I was used in preparing the paint for the final print.

Example 4 Example 1 was repeated except that the decorating Air-dryvehicle G was used paint for the first print was made using hot-meltvehicle A and the paint for the second print, which was superimposedover the first, was made using air-dry vehicle G. An excellent finaldecoration resulted upon firing the printed ware to fuse the decorationto the glass. Substantially the same results were obtained when hot-meltvehicle C was used in preparing the paint for the first print.

The ceramic decorating compositions, referred to in the examples aspaints will generally be prepared by suspending or dispersing theceramic decoration, such as a finely ground mixture of an inorganicpigment and glass, in either the hot-melt or air-dry vehicle inproportions of about 2 to 6 parts by weight of the decoration for eachpart of vehicle, the most usual proportions being about 4 to l.

The wax, mixture of waxes, or mixture of a wax with a wax-like material,used in the hot-melt vehicle should melt at a temperature within therange of 120 to 230 F. and constitute from 30 to 80%, preferably 40 to60%, of the vehicle. Examples of suitable waxes and wax-like materialswhich may be used either alone, in the case of certain waxes, or asmixtures to provide material melting Within the required temperaturerange are: parafiin, carnauba wax, spermaceti, beeswax, canawax,microcrystalline wax, palmitic acid, stearic acid and solid soaps.

The ethyl cellulose content of the hot-melt vehicle should be not lessthan about 1% nor greater than about and is preferably 1 to 5%. Itscontent in the preferred air-dry vehicles should be about 0.5 to about7%. The ethyl cellulose functions as a viscosifier or thickener and alsoas a hardening agent. In either type of vehicle low, medium or highviscosity ethyl cellulose may be used but the medium viscosity grade isgenerally preferred.

The amount of rosin or rosin derivative in the hotmelt vehicle should be14 to 68% and preferably 35 to 55%, Whereas the amount for the preferredair-dry vehicle is 15 to These materials serve in either type of vehicleas hardeners and facilitate adherence of the decoration print to theware. They also aid in rendering the ethyl cellulose miscible with thewax constituent of the hot-melt vehicle. Examples of these materialsare: rosin and abietic acid; rosin esters and esters of abietic acid,such as methyl abietate; polymerized rosin and polymerized abietic acid;hydrogenated rosin and hydrogenated abietic acid; and the metal salts ofrosin and of abietic acid, e. g., the zinc, titanium and calcium salts.The most preferred of these materials is hydrogenated rosin.

The hot-melt vehicle must contain from 0.5 to 10% of an organicphosphate material such as soya lecithin, heat-treated or cookedlecithin and phosphorated tall oil. One or both of these phosphatematerials, which function as wetting agents, will also be present in thepreferred air-dry vehicles, the amount being 0.5 to 10%. The preferredamount of lecithin in either type of vehicle is 4 to 10% whereas thepreferred amount of phosphorated tall oil is 0.5 to 7.0%. The use ofphosphorated tall oil is preferred.

Pyrogallic acid is not an essential ingredient of the hotmelt vehicle.However, its presence, e. g., in concentrations of 0.01 to 1%, appearsdesirable in some instances to inhibit undesired thickening of the hotvehicle or paint. Also, in the case of the preferred air-dry vehicle, itis frequently desirable, although not essential, that other substancesbe present in minor amounts as is indicated by the compositions shown inTable 2. Examples of such other substances whose presence may bedesirable to prevent the squeegee paints from gelling during preparationor storage, and the concentrations in which they generally will bepresent when used, are: diethyl oxalate, 1 to 5%; dl-malic acid, 0.1 to1%; boric acid, 0.4 to 0.6%; and 10% solution of 85% ortho phosphoricacid in pine oil, 1 to 10%.

The present method of employing a hot-melt vehicle in the application ofall but the last print decoration and of using an air-dry vehicle inapplying the last print, is

unique and results in definite and important advantages over methodsusing either type of vehicle in the application of all prints. Oneimportant advantage is that the use of driers, conventionally employedin all air-dry multiple-print methods, is entirely eliminated. Anotherimportant advantage is that the method permits anchoring the ware firmlyin an automatic decorating machine for all color applications therebysimplifying the problem of registration of multi-color designs andeliminating the necessity of molding a registration nib on the bottle asis now common practice. The present method further eliminates thenecessity for maintaining the stencil screen and paint for the finalprint at an elevated temperature as would be necessary if all printswere applied using hotmelt compositions. Also, the amount ofcarbonaceous material which must be burned off in the lehr is reduced ascompared to all hot-prints. Finally, there is less chance of damage topreceding prints when the final print is applied at room temperatureinstead of at an elevated temperature. Where only two prints are to beapplied the present method eliminates entirely the possibility of damageto the first print from the application of a succeeding hot composition.

Throughout the specification and in the appended claims the percentagevalues given are, unless otherwise specified, percentages by weightbased upon the total weight of the vehicle or decorating composition.

i claim:

1. A method of decorating a ceramic object comprising applying to saidobject by the squeegee method at least one print of a hot-melt ceramicdecorating composition while maintaining said composition at atemperature within the range 120 to 230 F. and while said object is atabout room temperature, said composition being nonvolatile and solid atroom temperature and nonsolid at said temperature within the range 120to 230 F., and said print being solidified instantly upon contact withsaid object, then superimposing on said print an airdry ceramicdecorating composition containing a volatile solvent and firing saidobject to fuse the decorations thereto, all of said decoratingcompositions containing 2 to 6 parts by weight of a ceramic decorationdispersed in one part of a vehicle, and said air-dry composition beingone which is non-solid at normal temperature and which solidifies uponthe removal of the volatile solvent therefrom by drying.

2. A method of decorating a ceramic object comprising applying at leastone decorating print of a hot-melt type ceramic decorating compositionby the squeegee method to said object while maintaining said compositionat a temperature within the range 120 to 230 F. and while said object isat a temperature at least 15 F. below the melting temperature of saidcomposition, said print solidifying instantly upon contacting saidobject, superimposing on said print; an air-dry type ceramic decoratingcomposition and then filing the object to fuse the decoration thereto,said hot-melt composition being non-volatile and solid at normaltemperature and comprising a dispersion of a ceramic decoration in avehicle in the proportion of 2 to 6 parts by weight of said ceramicdecoration per part of said vehicle, said vehicle containing: (a) 30 toof a material which melts within the temperature range to 230 F. and isfrom the group consisting of waxes, mixtures of waxes, and mixtures of awax with a material from the group consisting of palmitic acid, stearicacid and solid soaps; (b) 14 to 68% of a material from the groupconsisting of rosin and abietic acid, rosin esters and esters of abieticacid, polymerized rosin and polymerized abietic acid, hydrogenated rosinand hydrogenated abietic acid, and metal salts of rosin and of abieticacid; (c) 1 to 10% of ethyl cellulose; (d) 0.5 to 10% of an organicphosphate material from the group consisting of lecithin andphosphorated tall oil; and (e) 0 to 1% of pyrogallic acid, said air-drycomposition being non-solid at normal temperature and comprising adispersion of a ceramic decoration in a vehicle which includes avolatile solvent, said air-dry composition being one which solidifiesupon the removal of said volatile solvent therefrom by drying and whichcon tains 2 to 6 parts by weight of the ceramic decoration per part ofthe vehicle.

3. The method of claim 2 wherein the vehicle for the hot-meltcomposition contains: 40 to 60% of ingredient (a); 35 to 55% ofingredient (b); l to 5% of ingredient (c); 0.5 to 7% of ingredient (d),which is phosphorated tall oil; and to 1% of ingredient (e).

4. The method of claim 2 wherein the vehicle for the air-dry compositioncontains: (a) 50 to 80% of a volatile solvent; (b) 15 to 35% of amaterial from the group consisting of rosin and abietic acid, rosinesters and esters of abietic acid, polymerized rosin and polymerizedabietic acid, hydrogenated rosin and hydrogenated abietic acid, andmetal salts of rosin and of abietic acid; (c) 0.5 to 7% of ethylcellulose; and (d) 0.5 to 10% of an organic phosphate material of thegroup consisting of lecithin and phosphorated tall oil.

5. The method of claim 2 wherein the vehicle for the hot-metalcomposition contains: (a) 40 to 60% of a material which melts within thetemperature range 120 to 230 F. and is from the group consisting ofwaxes, mixtures of waxes, and mixtures of a wax with a material from thegroup consisting of palmitic acid, stearic acid and solid soaps; (b) 35to 55% of hydrogenated rosin; (c) 1 to 5% of ethyl cellulose; (d) 0.5 to7% of phosphorated tall oil and (e) O to 1% of pyrogallic acid, and thevehicle for the air-dry composition contains: (7) 50 to 80% of avolatile solvent; (g) 15 to 35 of a material from the group consistingof rosin and abietic acid, rosin esters and esters of abietic acid,polymerized rosin and polymerized abietic acid, hydrogenated rosin andhydrogenated abietic acid, and metal salts of rosin and of abietic acid;(h) 0.5 to 7% of ethyl cellulose; and (i) 0.5 to of a material of thegroup consisting of lecithin and phosphorated tall oil.

6. A method of decorating a ceramic object comprising applying ahot-melt type ceramic decorating composition by the squeegee method tosaid object while maintaining said composition at a temperature withinthe range 120 to 230 F. and while said object is at a temperature atleast F. below the melting temperature of said composition, whereby asolid, firm print is formed instantly upon contact of said compositionwith said object, and, without intermediate drying, superimposing onsaid print an air-dry type ceramic decorating composition and thenfiring the object to fuse the decoration thereto, said hotmeltcomposition being non-volatile and solid at normal temperature andcomprising a dispersion of a ceramic decoration in a vehicle in theproportion of 2 to 6 parts by weight of said ceramic decoration per partof said vehicle, said vehicle containing: (a) 40 to 60% of a materialwhich melts within the temperature range 120 to 230 F. and is from thegroup consisting of waxes, mix tures of waxes, and mixtures of a waxwith a material from the group consisting of palmitic acid, stearic acidand solid soaps; (b) 35 to 55 of a material from tht group consisting ofrosin and abietic acid, rosin esters and esters of abietic acid,polymerized rosin and polymerized abietic acid, hydrogenated rosin andhydrogenated abi tic acid, and metal salts of rosin and of abietic acid;(c) l to 5% of ethyl cellulose; (d) 0.5 to 7% of phosphorated tall oil;and (e) 0 to 1% of pyrogallic acid, said air-dry composition beingnon-solid at ordinary temperature and containing a volatile solvent, theremoval of which by drying causes the composition to solidify.

7. The method of claim 6 wherein the vehicle for the air-dry compositioncontains: (a) 50 to 80% of a volatile solvent; (b) 15 to 35% of amaterial from the group consisting of rosin and abietic acid, rosinesters and esters of abietic acid, polymerized rosin and polymerizedabietic 8 acid, hydrogenated rosin and hydrogenated abietic acid, andmetal salts of rosin and of abietic acid; (0) 0.5 to 7% of ethylcellulose; (d) 0.5 to 10% of an organic phosphate material of the groupconsisting of'lecithin and phosphorated tall oil.

8. A method of decorating a ceramic object comprising applying to saidobject a squeegee print of a hot-melt type decorating composition whilemaintaining said composition at a temperature within the range 120 to230 F. and while said object is at a temperature at least 15 F. belowthe melting temperature of said composition, whereby a solid, firm printis formed instantly upon contactof said composition with said objectand' superimposing on said print a squeegee print of an air-dry typedecorating composition, and then firing said object to fuse thedecoration thereto, said hot-melt composition being nonvolatile andsolid at normal temperature and comprising a dispersion of a ceramicdecoration, in a vehicle in the proportion of 2 to 6 parts by weight ofsaid ceramic decoration per part of said vehicle, said vehiclecontaining: (a) 30 to of a material which melts within the temperaturerange to 230 F. and is from the group consisting of waxes, mixtures ofwaxes, and mixtures of a wax with a material from the group consistingof palmitic acid, stearic acid and solid soaps; (b) 14 to 68% of amaterial from the group consisting of rosin and abietic acid, rosinesters and esters of abietic acid, polymerized rosin and polymerizedabietic acid, hydrogenated rosin and hydrogenated abietic acid, andmetal salts of rosin and of abietic acid; (0) 1 to 10% of ethylcelulose; (d) 0.5 to 10% of an organic phosphate material from the groupconsisting of lecithin and phosphorated tall oil; and (e) 0 to 1% ofpyrogallic acid, said air-dry composition being non-solid at normaltemperature and comprising a dispersion of a ceramic decoration in avehicle in the proportion of 2 to 6 parts by weight of the ceramicdecoration per part of the vehicle, the vehicle of said air-drycomposition containing: (7) 50 to 80% of a volatile solvent the removalof which by drying causes said air-dry composition to solidify; (g) 15to 35 of a material from the group consisting of rosin and abietic acid,rosin esters and esters of abietic acid, polymerized rosin andpolymerized abietic acid, hydrogenated rosin and hydrogenated abieticacid, and metal salts of rosin and of abietic acid; (11) 0.5 to 7% ofethyl cellulose; and (i) 0.5 to 10% of an organic phosphate material ofthe group consisting of lecithin and phosphorated tall oil.

9. A method of decorating a ceramic object comprising applying to saidobject at least one squeegee print of a hot-melt decorating compositionwhile maintaining said composition at a temperature .within the range120 to 230 F. and while said object is at a temperature at least 15 F.below the melting temperature of said composition, whereby a solid, firmprint is formed instantly upon contact of said composition with saidobject, superimposing on said print an air-dry ceramic decoratingcomposition and then firing the object to fuse the decoration thereto,said hot-melt composition being non-volatile and solid at normaltemperature and comprising a dispersion of a ceramic decoration in avehicle which contains:

(a) 30 to 80% of a wax which melts within the range V 120 to 230 F.; (b)14 to 68% of hydrogenated rosin; (c) 1 to 10% of ethyl cellulose; (cl)0.5 to 10% of an organic phosphate material from the group consisting oflecithin and phosphorated tall oil; and (e) 0 to 1% of pyrogallic acid,said air-dry composition being non-solid at normal temperature andcomprising a dispersion of a ceramic decoration in a vehicle whichincludes a volatile solvent whose removal by drying causes said air-drycomposition to solidify, all of said decorating compositions containing2 to 6 parts by weight of a ceramic decoration per part of the vehicle.

(References on iollowingpage) References Cited in the file of thispatent UNITED STATES PATENTS Huber Jan. 6, 1942 Huber Jan. 6, 1942 5Ellis et al. Mar. 3, 1942 Rummelsburg Dec. 15, 1942 10 2,318,124 ShurleyMay 4, 1943 2,390,123 Rietz et a1. Dec. 4, 1945 2,426,277 Miller Aug.26, 1947 OTHER REFERENCES Printing Inks, Ellis Reinhold PublishingCorp., 1940, pages 206 and 333 relied upon.

8. A METHOD OF DECORATING A CERAMIC OBJECT COMPRISING APPLYING TO SAIDOBJECT A SQUEEGEE PRINT OF A HOT-MELT TYPE DECORATING COMPOSITION WHILEMAINTAINING SAID COMPOSITION AT A TEMPERATURE WITHIN THE RANGE 120 TO230* F. AND WHILE SAID OBJECT IS AT A TEMPERATURE AT LEAST 15* F. BELOWTHE MELTING TEMPERATURE OF SAID COMPOSITION, WHEREBY A SOLID, FIRM PRINGIS FORMED INSTANTLY UPON CONTACT OF SAID COMPOSITION WITH SAID OBJECTAND SUPERIMPOSING ON SAID PRINT A SQUEEGEE PRING OF AN AIR-DRY TYPEDECORATING COMPOSITION, AND THEN FIRING SAID OBJECT TO FUSE THEDECORATION THERETO, SAID HOT-MELT COMPOSITION BEING NONVOLATILE ANDSOLID AT NORMAL TEMPERATURE AND COMPRISING A DISPERSIOIN OF A CERMAICDECORATION, IN A VEHICLE IN THE PROPORTION OF 2 TO 6 PARTS BY WEIGHT OFSAID CERAMIC DECORATION PER PART OF SAID VEHICLE, SAID VEHICLECONTAINING: (A) 30 TO 80% OF A MATERIAL WHICH MELTS WITHIN THETEMPERATURE RANGE 120 TO 230* F. AND IS FROM THE GROUP CONSISTING OFWAXES, MIXTURES OF WAXES, AND MIXTURES OF A WAX WITH A MATERIAL FROM THEGROUP CONSISTING OF PALMITIC ACID, STEARIC ACID AND SOLID SOAPS; (B) 14TO 68% OF A MATERIAL FROM THE GROUP CONSISTING OF ROSIN AND ABIETIC ACIDROSIN ESTERS AND ESTERS OF ABIETIC ACID, POLYMERIZED ROSIN ANDPOLYMERIZED ABIETIC ACID, HYDROGENATED ROSIN AND HYDROGENATED ABIETICACID, AND METAL SALTS OF ROSIN AND OF ABIETIC ACID; (C) 1 TO 10% OFEHTYL CELLULOSE; (D) 0.5 TO 10% OF AN ORGANIC PHOSPHATE MATERIAL FROMTHE GROUP CONSISTING OF LECITHIN AND PHOSPHORATED TALL OIL; AND (E) 0 TO1% OF PYROGALLIC ACID, SAID AIR-DRY COMPOSITION BEING NON-SOLID ATNORMAL TEMPERATURE AND COMPRISING A DISPERSION OF A CERAMIC DECORATIONIN A VEHICLE IN THE PROPORTION OF 2 TO 6 PARTS BY WEIGHT OF THE CERAMICDECORATION PER PART OF THE VEHICLE, THE VEHICLE OF SAID AIR-DRYCOMPOSITION CONTAINING: (F) 50 TO 80% OF A VOLATILE SOLVENT THE REMOVALOF WHICH BY DRYING CAUSES SAID AIR-DRY COMPOSITION TO SOLIDIFY; (G) 15TO 35% OF A MATERIAL FROM THE GROUP CONSISTING OF ROSIN AND ABIETICACID, ROSIN ESTERS AND ESTERS OF ABIETIC ACID, POLYMERIZED ROSIN ANDPOLYMERIZED ABIETIC ACID, HYDROGENATED ROSIN AND HYDROGENATED ABIETICACID, AND METAL SALTS OF ROSIN AND OF ABIETIC ACID; (H) 0.5 TO 7% OFETHYL CELLULOSE; AND (I) 0.5 TO 10% OF AN ORGANIC PHOSPHATE MATERIAL OFTHE GROUP CONSISTING OF LECITHIN AND PHOSPHORATED TALL OIL.